WO2023216131A1 - 钙钛矿太阳能电池及其制备方法 - Google Patents

钙钛矿太阳能电池及其制备方法 Download PDF

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WO2023216131A1
WO2023216131A1 PCT/CN2022/092191 CN2022092191W WO2023216131A1 WO 2023216131 A1 WO2023216131 A1 WO 2023216131A1 CN 2022092191 W CN2022092191 W CN 2022092191W WO 2023216131 A1 WO2023216131 A1 WO 2023216131A1
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layer
perovskite
covering
solar cell
covering layer
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PCT/CN2022/092191
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French (fr)
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陈长松
刘召辉
林维乐
林翔玲
梁伟风
涂保
陈国栋
郭永胜
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宁德时代新能源科技股份有限公司
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Priority to EP22924582.4A priority Critical patent/EP4300603A4/en
Priority to PCT/CN2022/092191 priority patent/WO2023216131A1/zh
Priority to CN202280056379.0A priority patent/CN117836957A/zh
Priority to US18/224,074 priority patent/US20230371290A1/en
Publication of WO2023216131A1 publication Critical patent/WO2023216131A1/zh

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    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
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    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
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    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
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    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present application relates to a perovskite solar cell.
  • the present application also relates to a preparation method of the perovskite solar cell.
  • a solar cell also known as a photovoltaic cell, is a device that directly converts light energy into electrical energy through the photoelectric effect or photochemical effect.
  • Perovskite cells are a new type of solar cell that is currently being widely studied. They have rapidly achieved high photoelectric conversion efficiency within a few years of their birth. Their maximum photoelectric conversion efficiency has exceeded 25%, and they have good application prospects.
  • perovskite solar cells Due to the great development of perovskite solar cells, higher requirements have been put forward for energy conversion efficiency and long-term stability.
  • existing perovskite films will have various intrinsic defects more or less during the preparation process.
  • the perovskite material itself is unstable and is easily prone to defects under the influence of light, heat, water, oxygen, etc. decomposes, thus affecting the performance of perovskite solar cells. Therefore, existing perovskite solar cells still need to be improved.
  • This application was made in view of the above-mentioned problems, and its purpose is to provide a perovskite solar cell with high energy conversion efficiency and good stability.
  • the first aspect of the present application provides a perovskite solar cell, which structurally includes a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer and a second electrode,
  • the perovskite layer includes a main perovskite layer and a one-dimensional perovskite coating layer covering its surface and surroundings.
  • the one-dimensional perovskite coating layer includes:
  • a first covering layer located between the main perovskite layer and the electron transport layer;
  • a second cladding layer located between the host perovskite layer and the hole transport layer.
  • the one-dimensional perovskite covering layer can inhibit ion migration, thereby reducing the degradation of perovskite by light;
  • the A-site ions in the one-dimensional perovskite covering layer are hydrophobic organic cations, which are not easily volatile and therefore have high stability.
  • the cations used as the covering layer material for the A-site ions have a strong interaction with the iodide ions in the host perovskite, which can form an interface anchor and inhibit the rotation of the B-X (such as Pb-I) octahedron, thereby improving the performance of the perovskite. phase stability;
  • the one-dimensional perovskite layer covers the surface of the main perovskite layer and forms an interface with it, it can improve the interface stability;
  • the one-dimensional perovskite covering layer can well block the erosion of external water, oxygen, and ultraviolet rays.
  • the one-dimensional perovskite cladding layer further includes a third cladding layer covering around the main perovskite layer.
  • the thickness of the first covering layer, the second covering layer, and the third covering layer are each independently 1 to 20 nm, optionally 2 to 5 nm.
  • the thickness of the first covering layer, the second covering layer and the third covering layer is within the above range, which can improve the photoelectric conversion efficiency of the perovskite solar cell.
  • the thickness of the first and second covering layers needs to be adjusted within the above range to balance the performance of the solar cell.
  • a passivation layer is optionally no longer used to passivate the host perovskite layer.
  • the absolute value of the difference between the LUMO energy level of the first covering layer and the LUMO energy level of the host perovskite layer is in the range of 0 to 0.3 eV, optionally in the range of 0.05 to 0.25 eV. .
  • the LUMO energy level of the first covering layer is greater than or equal to the LUMO energy level of the electron transport layer
  • the absolute value of the difference between the LUMO energy level of the first covering layer and the LUMO energy level of the electron transport layer is in the range of 0 to 0.6 eV, optionally in the range of 0.3 to 0.5 eV.
  • the LUMO energy levels between the first covering layer and the main perovskite layer, and between the first covering layer and the electron transport layer have the above-mentioned relationship, which is conducive to electrons reaching the electron transport layer from the perovskite layer more smoothly, thereby enabling It ensures the opening voltage of the battery and improves the photoelectric conversion efficiency of the solar cell.
  • the adjustment of the LUMO energy level of the first covering layer can also be achieved by adjusting its thickness and material.
  • the HOMO energy level of the second capping layer is greater than or equal to the HOMO energy level of the host perovskite layer
  • the absolute value of the difference between the HOMO energy level of the second covering layer and the HOMO energy level of the main perovskite layer is in the range of 0 to 0.3 eV, optionally in the range of 0.05 to 0.1 eV.
  • the HOMO energy level of the second capping layer is less than or equal to the HOMO energy level of the hole transport layer
  • the absolute value of the difference between the HOMO energy level of the second covering layer and the HOMO energy level of the hole transport layer is in the range of 0 to 0.3 eV, optionally in the range of 0 to 0.15 eV.
  • the HOMO energy levels between the second cladding layer and the main perovskite layer and between the second cladding layer and the hole transport layer have the above relationship, which is beneficial for holes to reach the hole transport layer from the perovskite layer more smoothly, thus It can ensure the opening voltage of the battery and affect the photoelectric conversion efficiency of the battery.
  • the covering materials of the first covering layer, the second covering layer and the third covering layer are each independently a halogen salt selected from at least one of the following substances or derivatives thereof:
  • the halogen salt can be iodide salt, bromide salt, chlorine salt, optionally iodide salt.
  • one of the first covering layer and the second covering layer is formed from the covering material and a halide metal salt, optionally, the molar ratio of the covering material and the halide metal salt is 1: Within the range of 0.9 ⁇ 1:1.3, optional within the range of 1:1.05 ⁇ 1:1.2.
  • the molar ratio of the covering material and the halide metal salt affects the energy level of the formed covering layer and thus affects the performance of the solar cell. Therefore, the energy level of the covering layer can be adjusted to achieve better performance by adjusting the molar ratio between the two, optionally, the molar ratio is within the above range.
  • the halide metal salt is selected from at least one of lead iodide, lead bromide or lead chloride, optionally lead iodide.
  • the second aspect of the present application provides a method for preparing a perovskite solar cell, including the steps of preparing or preparing a transparent electrode, the step of preparing an electron transport layer, the steps of preparing a perovskite layer, the steps of preparing a hole transport layer, preparing second electrode step, wherein,
  • the perovskite layer includes a main perovskite layer and a one-dimensional perovskite coating layer covering its surface and surroundings.
  • the one-dimensional perovskite coating layer includes:
  • a first covering layer located between the main perovskite layer and the electron transport layer;
  • a second cladding layer located between the host perovskite layer and the hole transport layer.
  • the step of preparing the perovskite layer includes the following operations:
  • any one of the bottom covering layer and the surface covering layer is a first covering layer, and the other one is a second covering layer.
  • the perovskite solar cells described in this application can be prepared using conventional technical means in the art.
  • at least one of the following methods is used to prepare the perovskite layer: chemical bath deposition method, electrochemical deposition method, chemical vapor deposition method, physical epitaxial growth method, co-evaporation method, atomic layer deposition method, precursor liquid spin coating method (spin coating), precursor liquid slit coating method, precursor liquid blade coating method, mechanical lamination method, etc.; among them, thermal evaporation method and precursor liquid coating (spin coating) method are optional.
  • the coating in (1) is performed by co-evaporation.
  • the coating in (2) is performed by evaporation.
  • the coating in (3) is performed by spin coating, and heating is performed after the spin coating is completed.
  • the method of preparing a perovskite solar cell further includes the step of preparing a third covering layer covering the periphery of the main perovskite layer. This step specifically includes the following operations:
  • the thickness of the protective layer is 1 to 10 nm.
  • a protective layer is used, which makes the preparation of the third covering layer more controllable and makes it easier to adjust the thickness and material.
  • the covering layer material in (1), (3), and (5) is each independently selected from at least one of the following substances or derivatives thereof Halogen salt:
  • the molar ratio of the covering material and the halide metal salt is in the range of 1:0.9 to 1:1.3, optionally in Within the range of 1:1.05 ⁇ 1:1.2.
  • the halide metal salt is selected from at least one of lead iodide, lead bromide or lead chloride, and optionally lead iodide.
  • the coating is performed by spin coating, co-evaporation or evaporation.
  • the coating is performed by spin coating, and the coating is performed after the spin coating is completed. Heat to get a protective layer.
  • the coating is performed by spin coating.
  • a solvent is used to dissolve the protective layer.
  • the solvent for dissolving the protective layer is trifluoroethanol; and then the protective layer and the materials on the protective layer are shaken off by rotating.
  • the protective layer material is lead pyridine-2-carboxylate.
  • a third aspect of the present application provides an electrical device, which includes the perovskite solar cell described in the present application or the perovskite solar cell prepared by the method of preparing a perovskite solar cell described in the present application.
  • Figure 1 is a schematic structural diagram of a perovskite solar cell. From bottom to top, it includes a transparent electrode (i.e., a first electrode), a charge transport layer, a perovskite main layer (i.e., a main perovskite layer), and a coating. It is surrounded by a one-dimensional perovskite coating layer, a charge transport layer, and a second electrode. The two charge transport layers are different and are respectively the electron transport layer or the hole transport layer.
  • This schematic diagram shows the one-dimensional perovskite coating layer. The coating fully covers the upper, lower and surrounding surfaces of the perovskite main layer.
  • Figure 2 is an X-ray diffraction pattern of the surface layer (second covering layer) of the one-dimensional perovskite coating layer prepared in Example I-1 of the present application.
  • the first two peaks in the figure are the one-dimensional perovskite coating layer.
  • structural peak, and the following peaks are all structural peaks of the main perovskite layer.
  • Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-6.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • step (c) means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c). , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
  • condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
  • the preparation of perovskite solar cells includes the preparation of perovskite layers.
  • the surface of usually prepared perovskite films will have more or less intrinsic defects such as vacancy defects, interstitial defects, anti-site defects, etc. These defects will cause component ions in the perovskite, especially at the A-site. Methylamine and formamidine ion migration, escape and degradation.
  • water, oxygen, ultraviolet light, etc. in the air or environment can pass through certain charge transport layers and reach the perovskite layer. Their contact with the perovskite may cause the perovskite to deteriorate and decompose.
  • the existence of these problems makes the structure of perovskite susceptible to damage and the failure of solar cell devices.
  • the key to solving the above problems is to suppress defects and ion migration on the perovskite surface and block water, oxygen, and ultraviolet rays in the environment. While achieving the above goals, the introduction of heterostructures should also be minimized. For example, the increase of heterogeneous interfaces and corresponding process flows should be avoided. Covering the surface of the host perovskite layer (for convenience of description, the uncovered three-dimensional perovskite layer will be referred to as the "host perovskite layer") with a one-dimensional perovskite cladding layer is an ideal solution to solve the above problems.
  • the intrinsic stability of the one-dimensional perovskite coating layer is superior, even higher than that of one-dimensional perovskite materials; at the same time, the one-dimensional perovskite coating layer covers the surface of the main perovskite and can block water, oxygen, and ultraviolet rays etc., and an interface is formed between it and the main perovskite layer, and the interface stability is improved.
  • fully covering the upper, lower and surrounding surfaces of the main perovskite layer can significantly improve the stability of perovskite solar cells.
  • the first aspect of the present application provides a perovskite solar cell, which structurally includes a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer and a second electrode,
  • the perovskite layer includes a main perovskite layer and a one-dimensional perovskite coating layer covering its surface and surroundings.
  • the one-dimensional perovskite coating layer includes:
  • a first covering layer located between the main perovskite layer and the electron transport layer;
  • a second cladding layer located between the host perovskite layer and the hole transport layer.
  • the perovskite solar cell described in this application may include a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode in order from bottom to top, or may include a transparent electrode, holes in order from top to bottom.
  • the transparent electrode is an electrode for light incidence. In this application, the transparent electrode is also called the first electrode.
  • perovskite structures can be divided into zero-dimensional, one-dimensional, two-dimensional and three-dimensional.
  • the preparation process of the one-dimensional perovskite covering layer is similar to that of the two-dimensional perovskite covering layer.
  • co-evaporated PbI 2 and propargyl ammonium iodide salt as an example, in the process of preparing the bottom covering layer using a thermal evaporation process, the solid powders of the two salts are used as the evaporation source, and under certain vacuum and temperature conditions The two salts are evaporated in molecular form, meet in the air or above the substrate, and undergo a chemical reaction to form a coplanar one-dimensional perovskite structure and deposit it on the substrate surface.
  • propargyl ammonium iodide is spin coated on the surface and surroundings of the main perovskite layer, and then heated and annealed, there is excess PbI in the main perovskite layer 2 is combined with propargyl ammonium iodide to form a one-dimensional perovskite structure.
  • one-dimensional perovskite covering layer Depending on the covering layer materials used, the structure of the resulting covering layer is very different, thus forming a one-dimensional perovskite covering layer and a two-dimensional perovskite covering layer.
  • the distinction between one-dimensional perovskite coating and two-dimensional perovskite coating can be determined using X-ray diffraction.
  • the formation mechanism of the one-dimensional perovskite coating is as follows: the cations of the coating material used serve as A-site cations, which induce octahedrons during the formation of the B-X (such as Pb-I) octahedral layered framework. A non-continuous coplanar arrangement is formed between them, and the mutual repulsion force between the space stacking of A-site cations is relatively large, so the distance between the B-X (such as Pb-I) octahedral framework is larger, forming a one-dimensional perovskite structure.
  • the one-dimensional perovskite covering layer can inhibit ion migration, thereby reducing the degradation of perovskite by light;
  • the A-site ions in the one-dimensional perovskite covering layer are hydrophobic organic cations, which are not easily volatile and therefore have high stability.
  • the cations used as the covering layer material for the A-site ions have a strong interaction with the iodide ions in the host perovskite, which can form an interface anchor and inhibit the rotation of the B-X (such as Pb-I) octahedron, thereby improving the performance of the perovskite. phase stability;
  • the one-dimensional perovskite layer covers the surface of the main perovskite layer and forms an interface with it, it can improve the interface stability;
  • the one-dimensional perovskite covering layer can well block the erosion of external water, oxygen, and ultraviolet rays.
  • the perovskite layer described in this application is suitable for matching with an electron transport layer or a hole transport layer that has poor blocking ability against water, oxygen, and ultraviolet rays.
  • the one-dimensional perovskite coating layer Compared with the two-dimensional perovskite coating layer, the one-dimensional perovskite coating layer has higher stability and stronger ability to block water and oxygen ultraviolet light. In addition, because it can cut off some connections such as iodine and lead, the conductive performance is poor. , so the thickness of the one-dimensional perovskite covering layer is required to be thinner.
  • Figure 2 is an X-ray diffraction pattern of the surface layer (second covering layer) of the one-dimensional perovskite coating layer prepared in Example I-1 of the present application, which confirms that what is formed in the present application is a one-dimensional perovskite coating layer. Cladding.
  • the one-dimensional perovskite cladding layer further includes a third cladding layer covering around the main perovskite layer.
  • the thicknesses of the first covering layer, the second covering layer, and the third covering layer are each independently 1 to 20 nm, optionally 2 to 5 nm.
  • the thickness of the first covering layer and the second covering layer is within the above range, which can improve the photoelectric conversion efficiency of the perovskite solar cell.
  • the thickness of the first and second covering layers needs to be adjusted within the above range to balance the performance of the solar cell.
  • a passivation layer is optionally no longer used to passivate the host perovskite layer.
  • the absolute value of the difference between the LUMO energy level of the first covering layer and the LUMO energy level of the host perovskite layer is in the range of 0 to 0.3 eV, optionally in the range of 0.05 to 0.25 eV. .
  • the LUMO energy level of the first covering layer is greater than or equal to the LUMO energy level of the electron transport layer
  • the absolute value of the difference between the LUMO energy level of the first covering layer and the LUMO energy level of the electron transport layer is in the range of 0 to 0.6 eV, optionally in the range of 0.3 to 0.5 eV.
  • the LUMO energy levels between the first covering layer and the main perovskite layer, and between the first covering layer and the electron transport layer have the above-mentioned relationship, which is conducive to electrons reaching the electron transport layer from the perovskite layer more smoothly, thereby enabling It ensures the opening voltage of the battery and improves the photoelectric conversion efficiency of the solar cell.
  • the adjustment of the LUMO energy level of the first covering layer can also be achieved by adjusting its thickness and material.
  • the HOMO energy level of the second capping layer is greater than or equal to the HOMO energy level of the host perovskite layer
  • the absolute value of the difference between the HOMO energy level of the second covering layer and the HOMO energy level of the main perovskite layer is in the range of 0 to 0.3 eV, optionally in the range of 0.05 to 0.1 eV.
  • the HOMO energy level of the second capping layer is less than or equal to the HOMO energy level of the hole transport layer
  • the absolute value of the difference between the HOMO energy level of the second covering layer and the HOMO energy level of the hole transport layer is in the range of 0 to 0.3 eV, optionally in the range of 0 to 0.15 eV.
  • the HOMO energy levels between the second cladding layer and the main perovskite layer and between the second cladding layer and the hole transport layer have the above relationship, which is beneficial for holes to reach the hole transport layer from the perovskite layer more smoothly, thus It can ensure the opening voltage of the battery and affect the photoelectric conversion efficiency of the battery.
  • the covering materials of the first covering layer, the second covering layer and the third covering layer are each independently a halogen salt selected from at least one of the following substances or derivatives thereof:
  • the halogen salt can be iodide salt, bromide salt, chlorine salt, optionally iodide salt.
  • the materials used for covering are in the form of ionic compounds.
  • the capping layer material can be made into the form of a salt (in theory, all salts that do not affect the operation are optional, preferably halogen salts), and then the salt is placed in direct contact with the host perovskite layer.
  • one of the first covering layer and the second covering layer is formed of the covering material and a halide metal salt.
  • the molar ratio of the covering material and the halide metal salt is 1: Within the range of 0.9 ⁇ 1:1.3, optional within the range of 1:1.05 ⁇ 1:1.2.
  • the molar ratio of the covering material and the halide metal salt affects the energy level of the formed covering layer and thus affects the performance of the solar cell. Therefore, the energy level of the covering layer can be adjusted to achieve better performance by adjusting the molar ratio between the two, optionally, the molar ratio is within the above range.
  • the other of the first covering layer and the second covering layer is formed of a covering layer materials without the use of halide metal salts.
  • the layer prepared first among the first covering layer and the second covering layer is the bottom layer.
  • the covering layer material and the halide metal salt are optionally used to form a layer by co-evaporation method.
  • dimensional perovskite structure secondly, the prepared layer is the surface layer.
  • only the covering layer material can be used without using halide metal salt.
  • X anion salts such as halide metal salts, can be used as appropriate in the preparation of the surface layer.
  • the halide metal salt is selected from at least one of lead iodide, lead bromide or lead chloride, optionally lead iodide.
  • the second aspect of the present application provides a method for preparing a perovskite solar cell, including the steps of preparing or preparing a transparent electrode, the step of preparing an electron transport layer, the steps of preparing a perovskite layer, the steps of preparing a hole transport layer, preparing second electrode step, wherein,
  • the perovskite layer includes a main perovskite layer and a one-dimensional perovskite coating layer covering its surface and surroundings.
  • the one-dimensional perovskite coating layer includes:
  • a first covering layer located between the main perovskite layer and the electron transport layer;
  • a second cladding layer located between the host perovskite layer and the hole transport layer.
  • the step of preparing the perovskite layer includes the following operations:
  • any one of the bottom covering layer and the surface covering layer is a first covering layer, and the other one is a second covering layer.
  • the perovskite solar cells described in this application can be prepared using conventional technical means in the art.
  • at least one of the following methods is used to prepare the perovskite layer: chemical bath deposition method, electrochemical deposition method, chemical vapor deposition method, physical epitaxial growth method, co-evaporation method, atomic layer deposition method, precursor liquid spin coating method (spin coating), precursor liquid slit coating method, precursor liquid blade coating method, mechanical lamination method, etc.; among them, thermal evaporation method and precursor liquid coating (spin coating) method are optional.
  • This application does not place specific restrictions on the preparation method of the perovskite layer, as long as the required purpose can be achieved.
  • the "coating" described in this application is performed using the above method.
  • the coating in (1) is performed by co-evaporation.
  • the "co-evaporation" described in this application can be carried out by using the powders of two or more substances as evaporation sources. Taking the formation of perovskite as an example, the powders of the corresponding substances are used as evaporation sources under certain vacuum and temperature conditions.
  • the evaporation source evaporates in the form of molecules. These molecules meet in the air or at the substrate, and a chemical reaction occurs to form a perovskite structure and deposit on the substrate surface.
  • the coating in (2) is performed by evaporation.
  • the coating in (3) is performed by spin coating, and heating is performed after the spin coating is completed.
  • the method of preparing a perovskite solar cell further includes the step of preparing a third covering layer covering the periphery of the main perovskite layer. This step specifically includes the following operations:
  • covering material and “covering material” are used synonymously.
  • a protective layer is used, which makes the preparation of the third covering layer more controllable and makes it easier to adjust the thickness and material.
  • the thickness of the protective layer is 1 to 10 nm.
  • the covering layer material in (1), (3), and (5) is each independently at least one selected from the following substances or derivatives thereof Halogen salt:
  • the molar ratio of the covering material and the halide metal salt is in the range of 1:0.9 to 1:1.3, optionally in Within the range of 1:1.05 ⁇ 1:1.2.
  • the halide metal salt is selected from at least one of lead iodide, lead bromide or lead chloride, optionally lead iodide.
  • the coating is performed by spin coating, co-evaporation or evaporation.
  • the coating is performed by spin coating, and the coating is performed after the spin coating is completed. Heat to get a protective layer.
  • the coating is performed by spin coating.
  • a solvent is used to dissolve the protective layer.
  • the solvent used to dissolve the protective layer is trifluoroethanol; and then the protective layer and the materials on the protective layer are shaken off by rotating.
  • the protective layer material is lead pyridine-2-carboxylate.
  • the protective layer when preparing the surrounding covering layer (ie, the third covering layer), the protective layer may not be used, and the surrounding covering layer may be prepared at the same time as the surface covering layer. At this time, the surface covering layer and the surrounding covering layer are The A-site ions are the same.
  • a specific operation example is as follows: When preparing the surface covering layer, add (can be added by spin coating) an excess of covering material solution (such as an isopropyl alcohol solution of propargyl ammonium iodide salt) so that it not only covers the main calcium
  • covering material solution such as an isopropyl alcohol solution of propargyl ammonium iodide salt
  • the titanium layer can also flow to the surroundings of the main perovskite layer and fully cover the surroundings, and then be heated and annealed, thereby obtaining a surface covering layer and surrounding covering layer in the form of one-dimensional perovskite at the same time.
  • perovskite solar cells also applies to the method of preparing perovskite solar cells.
  • a third aspect of the present application provides an electrical device, which includes the perovskite solar cell described in the present application or the perovskite solar cell prepared by the method of preparing a perovskite solar cell described in the present application.
  • the main perovskite layer, electron transport layer, hole transport layer and electrode structure of the perovskite solar cell are briefly described below, but the application is not limited thereto.
  • the material used to prepare the host perovskite is FAPbI 3 single crystal.
  • this application uses ABX 3 type host perovskite, where A is an inorganic or organic or organic-inorganic mixed cation, B is an inorganic or organic or organic-inorganic mixed cation, and X is an inorganic or organic or organic-inorganic mixed cation.
  • anions As an example, the ions at the A site can be, for example, methylamine cations MA + , formamidine cations FA + , Cs + and their mixtures; the B site ions can be, for example, Pb 2+ , Sn 2+ and their mixtures; X
  • the position ions can be halide ions, COO - and their mixtures.
  • the host perovskite layer can be prepared by evaporation (for example, FAPbI 3 single crystal).
  • the transparent electrode and the second electrode described in this application can be any electrode used in this field.
  • the electrode material of the transparent electrode and the second electrode is an organic or inorganic or organic-inorganic mixed conductive material.
  • the organic conductive material can be a conductive polymer, such as poly(3,4-ethylenedioxythiophene) (PEDOT), polythiophene, polyacetylene, etc.
  • the inorganic conductive material can be: a transparent conductive oxide, such as fluorine-doped Tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), etc.; metals; carbon derivatives, etc.
  • Transparent electrodes are used for light incidence.
  • transparent conductive oxides are used.
  • the transparent conductive oxide is composed of a glass substrate and a thin oxide (TCO for short) conductive layer.
  • TCO thin oxide
  • Commonly used TCOs include ITO, FTO, and AZO, but this application is not limited to these.
  • Conductive glass needs to be cleaned before use, such as ultrasonic cleaning with cleaning agents (including but not limited to surfactants), ethanol, acetone, isopropyl alcohol and deionized water.
  • the second electrode is used to collect carriers and is selected from metals or carbon derivatives.
  • the preparation method is a technical method known in the art, such as thermal evaporation method, and the thickness is 20-1000 nm.
  • metallic silver is the second electrode, which is made by evaporation method and has a thickness of 50 to 120 nm.
  • the hole transport layer is used to collect and extract holes from the perovskite layer. Any hole transport layer material commonly used in the art can be used, and hole transport layer materials that satisfy the above HOMO energy level matching relationship can optionally be used.
  • the material of the hole transport layer is at least one of the following materials and their derivatives: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]( PTAA), 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), poly-3-hexane Thiophene (P3HT), triptycene-core triphenylamine (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-aniline)carbazole-spirobis Fluorene (CzPAF-SBF), poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS), polythiophene, nickel oxide (NiOx), molybden
  • the thickness of the hole transport layer can range from 5-300nm, optionally from 100-200nm.
  • the electron transport layer is used to collect and extract electrons from the perovskite layer.
  • the electron transport layer material can be any electron transport layer material used in the art, and an electron transport layer material that satisfies the above HOMO energy level matching relationship can optionally be used.
  • the material of the electron transport layer is at least one of the following materials and their derivatives: [6,6]-phenyl-C 61 -butyric acid methyl ester (PC 61 BM), [6,6 ]-Phenyl-C 71 -methyl butyrate (PC 71 BM), fullerene C60 (C60), fullerene C70 (C70), tin dioxide (SnO 2 ), zinc oxide (ZnO), titanium dioxide ( TiO 2 ) etc.
  • the electron transport layer thickness range can be 5-200nm, optionally 20-100nm.
  • Both the hole transport layer and the electron transport layer can be prepared using methods commonly used in the art.
  • a glue leveler (LEBO EZ6-S, the same below) to spin-coat a 3 wt% SnO 2 nanocolloid aqueous solution on the FTO film layer of the transparent electrode.
  • the spin-coating time is 30 seconds. Then, it was heated on a constant temperature hot stage at a temperature of 150°C for 15 minutes to obtain an electron transport layer with a thickness of 30 nm.
  • the preparation process of the perovskite layer is as follows:
  • Step 1 Preparation of one-dimensional perovskite bottom layer (first covering layer)
  • Step 2 Preparing the host perovskite layer
  • Step 3 Preparation of one-dimensional perovskite surface layer (second covering layer)
  • a chlorobenzene solution of Spiro-OMeTAD with a concentration of 73 mg/mL was spin-coated on the obtained perovskite layer using a glue homogenizer at a speed of 5000 rpm.
  • the spin-coating time was 20 seconds to obtain a hole transport layer with a thickness of 150 nm.
  • the preparation of the perovskite solar cells implemented in I-2 to I-5 is similar to that of Example I-1, except for the preparation of the perovskite layer. See Table 1 for details.
  • the preparation of the perovskite solar cell in Implementation I-6 is the same as in Example I-1, except that the preparation of the perovskite layer is performed as follows after step 3:
  • Step 4 Add a protective layer
  • a glue leveler spin-coat a trifluoroethanol solution of lead pyridine-2-carboxylate with a concentration of 5 mg/mL on the one-dimensional perovskite surface layer prepared in step 3 at a speed of 5000 rpm, so that it completely covers the surface of the surface layer. , and then heated on a constant temperature hot stage at a temperature of 100°C for 10 minutes to obtain a protective layer.
  • Step 5 Add surrounding covering layer (third covering layer)
  • the preparation of the perovskite solar cell of Example I-15 is the same as that of Example I-1, except that the preparation of the perovskite layer is as follows:
  • the sample with the transparent electrode and electron transmission layer into the vacuum coating machine, and evaporate the FAPbI 3 bottom layer on the surface of the electron transmission layer under the vacuum condition of 5 ⁇ 10 -4 Pa.
  • the thickness is 500nm, and the evaporation source is FAPbI 3. single crystal to obtain a perovskite layer.
  • Examples II-1 to II-11 are similar to Example I-1, except for the preparation of the perovskite layer. See Table 2 for details.
  • Embodiments III-1 to III-9 are similar to Embodiment I-1, except for the preparation of the perovskite layer. See Table 3 for details.
  • the energy conversion efficiency of the perovskite solar cells of each Example and Comparative Example was measured.
  • the AM1.5G standard light source is used as the sunlight simulation light source, and a four-channel digital source meter (Keithley 2440) is used to measure the volt-ampere characteristic curve of the battery under the light source to obtain the battery's open circuit voltage Voc, short circuit current density Jsc, and filling factor.
  • FF Filt Factor
  • Pout, Popt, Vmpp, and Jmpp are the battery operating output power, incident light power, battery maximum power point voltage, and maximum power point current respectively.
  • the open circuit voltage Voc is the battery opening voltage in Table 2-3.
  • the perovskite solar cells in each example and comparative example were tested for stability performance. Place the battery in an air condition with a relative humidity of 75 to 80% and an ambient temperature of 25 to 30°C, without being protected from light, for at least 800 hours. According to the above test method, measure its energy conversion efficiency before and after placement, and calculate the 800 hours of placement. The ratio of the battery efficiency after hours to the initial efficiency is used as the battery stability performance parameter.
  • the energy band distribution of each covering layer was measured using an X-ray-UV photoelectron spectrometer (XPS-UPS) model Escalab 250Xi (from Thermo Scientific) under normal temperature and pressure.
  • XPS-UPS X-ray-UV photoelectron spectrometer
  • FIB focused ion beam
  • SEM high-resolution scanning electron microscope
  • the LUMO energy level of the bottom layer (first covering layer) of the one-dimensional perovskite cladding layer is related to its material. The smaller the molar ratio of the first covering layer material to lead iodide, the smaller the LUMO energy level;
  • the thickness of the one-dimensional perovskite bottom layer is 1 to 20 nm and the molar ratio of the bottom material to lead iodide is 1:1.0 to 1:1.2, better energy conversion efficiency and battery opening voltage can be achieved;
  • the LUMO energy level of the bottom layer of the one-dimensional perovskite cladding layer is greater than or less than, optionally less than the LUMO energy level of the main perovskite layer, and the absolute value of the difference between the two is in the range of 0 to 0.3 eV. When it is within the range of 0.05 ⁇ 0.25eV, it achieves better energy conversion efficiency and battery opening voltage;
  • the LUMO energy level of the electron transport layer is less than or equal to the LUMO energy level of the bottom layer (first covering layer) of the one-dimensional perovskite cladding layer, and the absolute value of the difference between the two is in the range of 0 to 0.6eV, optionally 0.3 Within the ⁇ 0.5eV range, better energy conversion efficiency and battery opening voltage are achieved.

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Abstract

本申请提供一种钙钛矿太阳能电池，其在结构上依次包括透明电极、电子传输层、钙钛矿层、空穴传输层和第二电极，其中所述钙钛矿层包括主体钙钛矿层及覆盖在其表面和四周的一维钙钛矿包覆层，所述一维钙钛矿包覆层包括：位于主体钙钛矿层和电子传输层之间的第一覆盖层；位于主体钙钛矿层和空穴传输层之间的第二覆盖层。本申请提供的钙钛矿太阳能电池能量转化效率高且稳定性好。

Description

钙钛矿太阳能电池及其制备方法 技术领域
本申请涉及一种钙钛矿太阳能电池。此外，本申请还涉及所述钙钛矿太阳能电池的制备方法。
背景技术
近年来，全球能源短缺和环境污染问题日益突出，太阳能电池作为理想的可再生能源受到越来越多的重视。太阳能电池，又称为光伏电池，是一种通过光电效应或光化学效应将光能直接转化为电能的装置。钙钛矿电池是目前广泛研究的一类新型太阳能电池，其在诞生后的几年内迅速获得了较高的光电转换效率，其最高光电转换效率已超过25％，具有良好的应用前景。
由于钙钛矿太阳能电池取得了极大的发展，因此对能量转换效率和长期稳定性等也提出了更高的要求。然而，现有的钙钛矿薄膜在制备过程中或多或少都会出现各种本征缺陷，此外，钙钛矿材料本身不稳定，在光、热、水、氧等的影响下极易发生分解，因而影响钙钛矿太阳能电池的性能。因此，现有的钙钛矿太阳能电池仍有待改进。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种能量转换率高且稳定性好的钙钛矿太阳能电池。
为了实现上述目的，本申请的第一方面提供了一种钙钛矿太阳能电池，其在结构上依次包括透明电极、电子传输层、钙钛矿层、空穴传输层和第二电极，
其中所述钙钛矿层包括主体钙钛矿层及覆盖在其表面和四周的一维钙钛矿包覆层，所述一维钙钛矿包覆层包括：
位于主体钙钛矿层和电子传输层之间的第一覆盖层；
位于主体钙钛矿层和空穴传输层之间的第二覆盖层。
使用一维钙钛矿层对主体钙钛矿层进行上下表面包覆具有以下优势：
(1)一维钙钛矿覆盖层能够抑制离子迁移，从而降低光对钙钛矿的降解作用；
(2)一维钙钛矿覆盖层的形成能低，故本征稳定性高；
(3)一维钙钛矿覆盖层中作为A位离子的是疏水有机阳离子，不易挥发，因此稳定性较高。
(4)作为A位离子的覆盖层材料的阳离子与主体钙钛矿中的碘离子具有强作用力，能够形成界面锚定，抑制B-X(例如Pb-I)八面体旋转，从而提高钙钛矿的相稳定性；
(5)一维钙钛矿层在覆盖在主体钙钛矿层表面并与之形成界面时，能够提高界面稳定性；
(6)一维钙钛矿覆盖层能够很好地阻隔外界水、氧、紫外线的侵蚀。
在任意实施方式中，所述一维钙钛矿包覆层还包括覆盖主体钙钛矿层四周的第三覆盖层。
对主体钙钛矿层进行全面的包覆，即，上下表面及四周全覆盖，相比于仅上下表面覆盖的钙钛矿，所得到的电池器件能够实现更好的长期稳定性。
在任意实施方式中，所述第一覆盖层、所述第二覆盖层、所述第三覆盖层的厚度各自独立地为1～20nm，可选2～5nm。
第一层覆盖层、第二层覆盖层和第三层覆盖层的厚度在上述范围内，能够提高钙钛矿太阳能电池的光电转化效率。
另外，由于形成的一维钙钛矿的本征电阻较大，因此需要在上述范围内调控第一、第二覆盖层的厚度来平衡太阳能电池的性能。
在使用了本申请所述的一维钙钛矿包覆层之后，可选地不再使用钝化层来对主体钙钛矿层进行钝化。
在任意实施方式中，所述第一覆盖层的LUMO能级与所述主体钙钛矿层的LUMO能级之差的绝对值在在0～0.3eV范围内，可选在0.05～0.25eV范围内。
在任意实施方式中，所述第一覆盖层的LUMO能级大于或等于所述电子传输层的LUMO能级，且
所述第一覆盖层的LUMO能级与所述电子传输层的LUMO能级之差的绝对值在0～0.6eV范围内，可选在0.3～0.5eV范围内。
第一覆盖层和主体钙钛矿层之间、第一覆盖层和电子传输层之间的LUMO能级具有如上所述的关系，有利于电子更顺利地从钙钛矿层到达电子传输层，从而能够保证电池开压，并且能够改善太阳能电池的光电转化效率。
所述第一覆盖层的LUMO能级的调节还可通过调节其厚度和材料来实现。
在任意实施方式中，所述第二覆盖层的HOMO能级大于或等于所述主体钙钛矿层的HOMO能级，且
所述第二覆盖层的HOMO能级与所述主体钙钛矿层的HOMO能级之差的绝对值在0～0.3eV范围内，可选在0.05～0.1eV范围内。
在任意实施方式中，所述第二覆盖层的HOMO能级小于或等于所述空穴传输层的HOMO能级，且
所述第二覆盖层的HOMO能级与所述空穴传输层的HOMO能级之差的绝对值在0～0.3eV范围内，可选在0～0.15eV范围内。
第二覆盖层和主体钙钛矿层之间以及第二覆盖层和空穴传输层之间的HOMO能级具有如上的关系，有利于空穴更顺利地从钙钛矿层到达空穴传输层，从而能够保证电池开压，并且能够影响电池的光电转化效率。
在任意实施方式中，所述第一覆盖层、所述第二覆盖层和所述第三覆盖层的覆盖材料各自独立地为选自以下物质或其衍生物中的至少一种的卤素盐：
1-(2-吡啶基)-1H-吡唑、碘化吡咯烷、炔丙基铵阳离子、四丁基铵阳离子、2-氯代三乙铵阳离子。
所述卤素盐可为碘盐、溴盐、氯盐，可选为碘盐。
在任意实施方式中，所述第一覆盖层和所述第二覆盖层之一由所述覆盖材料和卤化金属盐形成，可选地，所述覆盖材料和卤化金属盐的摩尔比在1:0.9～1:1.3范围内，可选在1:1.05～1:1.2范围内。
覆盖材料和卤化金属盐的摩尔比影响所形成的覆盖层的能级进而影响太阳能电池的性能。因此可通过调节这二者的摩尔比来调节覆盖层的能级以实现更好的性能，可选地，所述摩尔比在上述范围内。
在任意实施方式中，所述卤化金属盐选自碘化铅、溴化铅或氯化铅中的至少一种，可选为碘化铅。
本申请的第二方面提供一种制备钙钛矿太阳能电池的方法，包括制备或准备透明电极的步骤、制备电子传输层的步骤、制备钙钛矿层的步骤、制备空穴传输层的步骤、制备第二电极的步骤，其中，
所述钙钛矿层包括主体钙钛矿层及覆盖在其表面和四周的一维钙钛矿包覆层，所述一维钙钛矿包覆层包括：
位于主体钙钛矿层和电子传输层之间的第一覆盖层；
位于主体钙钛矿层和空穴传输层之间的第二覆盖层。
在任意实施方式中，所述制备钙钛矿层的步骤包括以下操作：
(1)在电子传输层或空穴传输层上涂覆覆盖层材料以及卤化金属盐，得到底层覆盖层，
(2)在底层覆盖层上涂覆用于制备主体钙钛矿的材料，得到主体钙钛矿层，
(3)在主体钙钛矿层上涂覆覆盖层材料，得到表层覆盖层，
其中所述底层覆盖层和所述表层覆盖层中任意一个为第一覆盖层，另一个为第二覆盖层。
本申请所述的钙钛矿太阳能电池可采用本领域常规技术手段制备。可选地，采用以下至少一种方法制备钙钛矿层：化学浴沉积方法、电化学沉积方法、化学气相沉积方法、物理外延生长方法、共蒸镀方 法、原子层沉积方法、前驱液旋涂方法(旋涂)、前驱液狭缝涂布方法、前驱液刮涂方法、机械压合方法等；其中，可选热蒸镀方法及前驱液涂布(旋涂)方法。
可选地，(1)中的涂覆采用共蒸镀方式进行。
可选地，(2)中的涂覆采用蒸镀方式进行。
可选地，(3)中的涂覆采用旋涂方式进行，旋涂完毕后进行加热。
在任意实施方式中，所述制备钙钛矿太阳能电池的方法还包括制备覆盖主体钙钛矿层四周的第三覆盖层的步骤，该步骤具体包括以下操作：
(4)在表层覆盖层上涂覆保护层材料，得到保护层，
(5)在保护层上添加覆盖层材料的溶液，使之流动到主体钙钛矿层和保护层的四周以完全覆盖所述四周，加热，得到四周覆盖层，此即为第三覆盖层，
(6)除去保护层。
可选地，保护层厚度为1～10nm。
可选地，在制备钙钛矿太阳能电池的第三覆盖层时，采用保护层，使得第三覆盖层的制备更可控，也更容易进行厚度和材料的调整。
在任意实施方式中，在制备钙钛矿太阳能电池的方法中，(1)、(3)、(5)中的覆盖层材料各自独立地为选自以下物质或其衍生物中的至少一种的卤素盐：
1-(2-吡啶基)-1H-吡唑、碘化吡咯烷、炔丙基铵阳离子、四丁基铵阳离子、2-氯代三乙铵阳离子。
在任意实施方式中，在制备钙钛矿太阳能电池的方法中，在(1)中，所述覆盖材料和所述卤化金属盐的摩尔比在1:0.9～1:1.3范围内，可选在1:1.05～1:1.2范围内。
在任意实施方式中，在制备钙钛矿太阳能电池的方法中，所述卤化金属盐选自碘化铅、溴化铅或氯化铅中的至少一种，可选为碘化铅。
在任意实施方式中，所述涂覆以旋涂、共蒸镀或蒸镀的方式进行，可选地，在(4)中，所述涂覆以旋涂的方式进行，旋涂完毕后进行加热，得到保护层。
可选地，(5)-(6)中，所述涂覆以旋涂的方式进行。
在任意实施方式中，在(6)中，使用溶剂溶解保护层，可选地，溶解保护层的溶剂为三氟乙醇；然后将保护层及保护层上面的物质通过旋转的方式甩去。
在任意实施方式中，所述保护层材料为吡啶-2-羧酸铅。
本申请的第三方面提供一种用电装置，其包括本申请所述的钙钛矿太阳能电池或本申请所述的制备钙钛矿太阳能电池的方法制备的钙钛矿太阳能电池。
附图说明
图1为钙钛矿太阳能电池的结构示意图，图中从下到上依次包括透明电极(即，第一电极)、电荷传输层、钙钛矿主体层(即，主体钙钛矿层)及包覆其四周的一维钙钛矿包覆层、电荷传输层、第二电极，其中两个电荷传输层不同，分别为电子传输层或空穴传输层；此示意图示出了一维钙钛矿包覆层对钙钛矿主体层的上下表面及四周的全面包覆。
图2为本申请实施例I-1中制备的一维钙钛矿包覆层的表层(第二覆盖层)的X射线衍射图，图中前两个峰为一维钙钛矿包覆层的结构峰，后面的峰均为主体钙钛矿层的结构峰。
具体实施方式
以下，适当地参照附图详细说明具体公开了钙钛矿太阳能电池的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理 解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-6。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，可选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
钙钛矿太阳能电池的制备包括钙钛矿层的制备。然而，通常制备的钙钛矿薄膜的表面或多或少都会出现空位缺陷、间隙缺陷、反位缺陷等本征缺陷，这些缺陷会引起钙钛矿中的组分离子、特别是A位上的甲胺、甲脒离子迁移、逸出与降解。此外，空气或环境中的水、氧、紫外线等可穿过某些电荷传输层，到达钙钛矿层，它们与钙钛矿接触可能会造成钙钛矿的变质、分解。这些问题的存在使得钙钛矿的结构容易遭到破坏并且容易使太阳能电池器件失效。
经过对上述问题的研究，现认为抑制钙钛矿表面的缺陷和离子迁移、阻隔环境中的水、氧、紫外线等解决上述问题的关键。在实现上述目标的同时，还应尽量减少异质结构的引入，例如，应避免增加异质界面与相应的工艺流程。在主体钙钛矿层(为方便描述，下文将未被覆盖的三维钙钛矿层称为“主体钙钛矿层”)表面覆盖一维钙钛矿包覆层是解决上述问题的一种理想方案。一维钙钛矿包覆层的本征稳定性优越，甚至高于一维钙钛矿材料；同时，一维钙钛矿包覆层覆盖在主体钙钛矿表面，能够阻隔水、氧、紫外线等，并且其与主体钙钛矿层之间形成界面，界面稳定性提高。此外，对主体钙钛矿层进行上下表面及四周全覆盖能够显著改善钙钛矿太阳能电池的稳定性。
因此，本申请的第一方面提供一种钙钛矿太阳能电池，其在结构上依次包括透明电极、电子传输层、钙钛矿层、空穴传输层和第二电极，
其中所述钙钛矿层包括主体钙钛矿层及覆盖在其表面和四周的一维钙钛矿包覆层，所述一维钙钛矿包覆层包括：
位于主体钙钛矿层和电子传输层之间的第一覆盖层；
位于主体钙钛矿层和空穴传输层之间的第二覆盖层。
本申请所述的钙钛矿太阳能电池从下到上可依次包括透明电极、电子传输层、钙钛矿层、空穴传输层、第二电极，也可从上到下依次包括透明电极、空穴传输层、钙钛矿层、电子传输层、第二电极，如图1所示，太阳光从下方射入。透明电极为用于光入射的电极。本申请中，透明电极也称作第一电极。
从空间维度结构来讲，钙钛矿结构可以分为零维、一维、二维和三维。
一维钙钛矿覆盖层的制备工艺与二维钙钛矿覆盖层的制备工艺方法相近。以共蒸PbI 2和炔丙基铵碘盐为例，在例如采用热蒸镀工艺制备底层覆盖层的过程中，以两种的盐的固体粉末为蒸发源，在一定真空度与温度条件下使两种盐以分子形式蒸发，在空中或上方衬底相遇，发生化合反应形成共面一维钙钛矿结构并沉积在衬底表面。在采用例如旋涂工艺制备表层覆盖层及四周覆盖层的过程中，旋涂例如炔丙基铵碘盐于主体钙钛矿层表面和四周，再进行加热退火，主体钙钛矿层中存在过量的PbI 2与炔丙基铵碘盐化合构成一维钙钛矿结构。
采用的覆盖层材料不同，所得到的覆盖层的结构有很大不同，由此形成一维钙钛矿覆盖层和二维钙钛矿覆盖层。一维钙钛矿覆盖层和二维钙钛矿覆盖层的区分可采用X射线衍射法进行确定。
现认为，一维钙钛矿覆盖层的形成机理如下：所使用的覆盖层材料的阳离子作为A位阳离子，其在B-X(例如Pb-I)八面体层状框架形成的过程中，诱导八面体间形成非连续共面排布，且A位阳离子间空间堆叠方式互斥力较大，因而B-X(例如Pb-I)八面体框架间隔较大，形成进而一维钙钛矿结构。
使用一维钙钛矿层对主体钙钛矿层进行上下表面包覆具有以下优势：
(1)一维钙钛矿覆盖层能够抑制离子迁移，从而降低光对钙钛矿的降解作用；
(2)一维钙钛矿覆盖层的形成能低，故本征稳定性高；
(3)一维钙钛矿覆盖层中作为A位离子的是疏水有机阳离子，不易挥发，因此稳定性较高。
(4)作为A位离子的覆盖层材料的阳离子与主体钙钛矿中的碘离子具有强作用力，能够形成界面锚定，抑制B-X(例如Pb-I)八面体旋转，从而提高钙钛矿的相稳定性；
(5)一维钙钛矿层在覆盖在主体钙钛矿层表面并与之形成界面时，能够提高界面稳定性；
(6)一维钙钛矿覆盖层能够很好地阻隔外界水、氧、紫外线的侵蚀。
因此，本申请所述的钙钛矿层适合与对水、氧、紫外线阻挡能力较差的电子传输层或空穴传输层搭配。
与二维钙钛矿覆盖层相比，一维钙钛矿覆盖层稳定性更高，阻隔水氧紫外光能力更强，另外，由于其能够隔断了一些例如碘铅连接，因此导电性能较差，因而一维钙钛矿覆盖层的厚度要求更薄一些。
图2中为本申请实施例I-1中制备的一维钙钛矿包覆层的表层(第二覆盖层)的X射线衍射图，证实了本申请中形成的是一维钙钛矿包覆层。
在一些实施方式中，所述一维钙钛矿包覆层还包括覆盖主体钙钛矿层四周的第三覆盖层。
对主体钙钛矿层进行全面的包覆，即，上下表面及四周全覆盖，相比于仅上下表面覆盖的钙钛矿，所得到的电池器件能够实现更好的长期稳定性。
在一些实施方式中，所述第一覆盖层、所述第二覆盖层、所述第三覆盖层的厚度各自独立地为1～20nm，可选2～5nm。
第一层覆盖层和第二层覆盖层的厚度在上述范围内，能够提高钙钛矿太阳能电池的光电转化效率。
另外，由于形成的一维钙钛矿的本征电阻较大，因此需要在上述范围内调控第一、第二覆盖层的厚度来平衡太阳能电池的性能。
在使用了本申请所述的一维钙钛矿包覆层之后，可选地不再使用钝化层来对主体钙钛矿层进行钝化。
在一些实施方式中，所述第一覆盖层的LUMO能级与所述主体钙钛矿层的LUMO能级之差的绝对值在在0～0.3eV范围内，可选在0.05～0.25eV范围内。
在一些实施方式中，所述第一覆盖层的LUMO能级大于或等于所述电子传输层的LUMO能级，且
所述第一覆盖层的LUMO能级与所述电子传输层的LUMO能级之差的绝对值在0～0.6eV范围内，可选在0.3～0.5eV范围内。
第一覆盖层和主体钙钛矿层之间、第一覆盖层和电子传输层之间的LUMO能级具有如上所述的关系，有利于电子更顺利地从钙钛矿层到达电子传输层，从而能够保证电池开压，并且能够改善太阳能电池的光电转化效率。
所述第一覆盖层的LUMO能级的调节还可通过调节其厚度和材料来实现。
在一些实施方式中，所述第二覆盖层的HOMO能级大于或等于所述主体钙钛矿层的HOMO能级，且
所述第二覆盖层的HOMO能级与所述主体钙钛矿层的HOMO能级之差的绝对值在0～0.3eV范围内，可选在0.05～0.1eV范围内。
在一些实施方式中，所述第二覆盖层的HOMO能级小于或等于所述空穴传输层的HOMO能级，且
所述第二覆盖层的HOMO能级与所述空穴传输层的HOMO能级之差的绝对值在0～0.3eV范围内，可选在0～0.15eV范围内。
第二覆盖层和主体钙钛矿层之间以及第二覆盖层和空穴传输层之间的HOMO能级具有如上的关系，有利于空穴更顺利地从钙钛矿层到达空穴传输层，从而能够保证电池开压，并且能够影响电池的光电转化效率。
在一些实施方式中，所述第一覆盖层、所述第二覆盖层和所述第三覆盖层的覆盖材料各自独立地为选自以下物质或其衍生物中的至少一种的卤素盐：
1-(2-吡啶基)-1H-吡唑、碘化吡咯烷、炔丙基铵阳离子、四丁基铵阳离子、2-氯代三乙铵阳离子。
所述卤素盐可为碘盐、溴盐、氯盐，可选为碘盐。
实际操作中，用于覆盖的材料为离子化合物形式。可将覆盖层材料做成盐的形式(理论上所有不影响操作的盐皆是可选的，最佳为卤素盐)，然后使所述盐与主体钙钛矿层直接接触。
在一些实施方式中，所述第一覆盖层和所述第二覆盖层之一由所述覆盖材料和卤化金属盐形成，可选地，所述覆盖材料和卤化金属盐的摩尔比在1:0.9～1:1.3范围内，可选在1:1.05～1:1.2范围内。
覆盖材料和卤化金属盐的摩尔比影响所形成的覆盖层的能级进而影响太阳能电池的性能。因此可通过调节这二者的摩尔比来调节覆盖层的能级以实现更好的性能，可选地，所述摩尔比在上述范围内。
在所述第一覆盖层和所述第二覆盖层之一由上述覆盖材料和卤化金属盐形成的情况下，所述第一覆盖层和所述第二覆盖层中的另一层由覆盖层材料来制备，无需使用卤化金属盐。实际操作中，所述第一覆盖层和所述第二覆盖层中先制备的一层为底层，在底层制备过程中，使用覆盖层材料和卤化金属盐可选地采用共蒸镀方法形成一维钙钛矿结构；其次制备的一层为表层，在表层制备过程中，可以仅使用覆盖层材料无需使用卤化金属盐，这是因为制备好的主体钙钛矿层中通常存在多余的X阴离子，其可与覆盖层材料相互作用形成表层覆盖层。在制备的主体钙钛矿层中不存在多余X阴离子或者存在的X阴离子不足的情况下，可在表层制备中酌情使用X阴离子盐，例如卤化金属盐。
在一些实施方式中，所述卤化金属盐选自碘化铅、溴化铅或氯化铅中的至少一种，可选为碘化铅。
本申请的第二方面提供一种制备钙钛矿太阳能电池的方法，包括制备或准备透明电极的步骤、制备电子传输层的步骤、制备钙钛矿层的步骤、制备空穴传输层的步骤、制备第二电极的步骤，其中，
所述钙钛矿层包括主体钙钛矿层及覆盖在其表面和四周的一维钙钛矿包覆层，所述一维钙钛矿包覆层包括：
位于主体钙钛矿层和电子传输层之间的第一覆盖层；
位于主体钙钛矿层和空穴传输层之间的第二覆盖层。
在一些实施方式中，所述制备钙钛矿层的步骤包括以下操作：
(1)在电子传输层或空穴传输层上涂覆覆盖层材料以及卤化金属盐，得到底层覆盖层，
(2)在底层覆盖层上涂覆用于制备主体钙钛矿的材料，得到主体钙钛矿层，
(3)在主体钙钛矿层上涂覆覆盖层材料，得到表层覆盖层，
其中所述底层覆盖层和所述表层覆盖层中任意一个为第一覆盖层，另一个为第二覆盖层。
本申请所述的钙钛矿太阳能电池可采用本领域常规技术手段制备。可选地，采用以下至少一种方法制备钙钛矿层：化学浴沉积方法、电化学沉积方法、化学气相沉积方法、物理外延生长方法、共蒸镀方法、原子层沉积方法、前驱液旋涂方法(旋涂)、前驱液狭缝涂布方法、前驱液刮涂方法、机械压合方法等；其中，可选热蒸镀方法及前驱液涂布(旋涂)方法。本申请对钙钛矿层的制备方法不做具体限制，只要能实现所需目的即可。可选地，本申请所述的“涂覆”采用上述方法来进行。
可选地，(1)中的涂覆采用共蒸镀方式进行。本申请所述的“共蒸镀”可以通过以两种以上的物质的粉末作为蒸发源中来进行，以钙钛矿的形成为例，在一定真空度与温度条件下使相应物质的粉末作为蒸发源以分子形式蒸发，这些分子在空中或衬底处相遇，发生化合反应形成钙钛矿结构并沉积在衬底表面。
可选地，(2)中的涂覆采用蒸镀方式进行。
可选地，(3)中的涂覆采用旋涂方式进行，旋涂完毕后进行加热。
在一些实施方式中，所述制备钙钛矿太阳能电池的方法还包括制备覆盖主体钙钛矿层四周的第三覆盖层的步骤，该步骤具体包括以下操作：
(4)在表层覆盖层上涂覆保护层材料，得到保护层，
(5)在保护层上添加覆盖层材料的溶液，使之流动到主体钙钛矿层和保护层的四周以完全覆盖所述四周，加热，得到四周覆盖层，此即为第三覆盖层，
(6)除去保护层。
本申请中，“覆盖层材料”和“覆盖材料”同义使用。
可选地，在制备钙钛矿太阳能电池的第三覆盖层时，采用保护层，使得第三覆盖层的制备更可控，也更容易进行厚度和材料的调整。
可选地，保护层厚度为1～10nm。
在一些实施方式中，在制备钙钛矿太阳能电池的方法中，(1)、(3)、(5)中的覆盖层材料各自独立地为选自以下物质或其衍生物中的至少一种的卤素盐：
1-(2-吡啶基)-1H-吡唑、碘化吡咯烷、炔丙基铵阳离子、四丁基铵阳离子、2-氯代三乙铵阳离子。
在一些实施方式中，在制备钙钛矿太阳能电池的方法中，在(1)中，所述覆盖材料和所述卤化金属盐的摩尔比在1:0.9～1:1.3范围内，可选在1:1.05～1:1.2范围内。
在一些实施方式中，在制备钙钛矿太阳能电池的方法中，所述卤化金属盐选自碘化铅、溴化铅或氯化铅中的至少一种，可选为碘化铅。
在一些实施方式中，所述涂覆以旋涂、共蒸镀或蒸镀的方式进行，可选地，在(4)中，所述涂覆以旋涂的方式进行，旋涂完毕后进行加热，得到保护层。
可选地，(5)-(6)中，所述涂覆以旋涂的方式进行。
在一些实施方式中，在(6)中，使用溶剂溶解保护层，可选地，溶解保护层的溶剂为三氟乙醇；然后将保护层及保护层上面的物质通过旋转的方式甩去。
在一些实施方式中，所述保护层材料为吡啶-2-羧酸铅。
在一些可选实施方式中，在制备四周覆盖层(即第三覆盖层)时，可不使用保护层，可在制备表层覆盖层的同时制备四周覆盖层，此时表层覆盖层和四周覆盖层的A位离子相同。一个具体的操作实例如下：在制备表层覆盖层时添加(可采用旋涂的方式添加)过量的覆盖材料的溶液(例如炔丙基铵碘盐的异丙醇溶液)，使之不仅覆盖主体钙钛矿层还能够流动到主体钙钛矿层的四周并且对四周全面覆盖，然后加热退火，从而同时得到一维钙钛矿形式的表层覆盖层和四周覆盖层。
本申请中，针对钙钛矿太阳能电池的描述也适用于制备钙钛矿太阳能电池的方法。
本申请的第三方面提供一种用电装置，其包括本申请所述的钙钛矿太阳能电池或本申请所述的制备钙钛矿太阳能电池的方法制备的钙钛矿太阳能电池。
下面简述钙钛矿太阳能电池的主体钙钛矿层、电子传输层、空穴传输层和电极结构，但本申请不限于此。
主体钙钛矿层
可使用本领域中常规使用的任何钙钛矿材料制备。可选地，用于制备主体钙钛矿的材料为FAPbI 3单晶。
可选地，本申请使用ABX 3型的的主体钙钛矿，其中，A为无机或有机或有机无机混合阳离子，B为无机或有机或有机无机混合阳离子，X为无机或有机或有机无机混合阴离子。作为示例，A位离子可为，例如甲胺阳离子MA +、甲脒阳离子FA +、Cs +以及它们的混合；B位离子可为，例如，Pb 2+、Sn 2+以及它们的混合；X位离子，可为卤素离子、COO -以及它们的混合。
可选地，可通过蒸镀(例如FAPbI 3单晶)的方式来制备主体钙钛矿层。
透明电极和第二电极
本申请所述的透明电极、第二电极可为本领域中使用的任何电极。可选地，所述的透明电极、第二电极的电极材料为有机或无机或有机无机混合的导电材料。作为示例，有机导电材料可为导电聚合物，例如，聚(3,4-乙烯二氧噻吩)(PEDOT)、聚噻吩、聚乙炔等；无机导电材料可为：透明导电氧化物，例如掺氟的氧化锡(FTO)、氧化铟锡(ITO)、铝掺杂的氧化锌(AZO)等；金属；碳衍生物等。
透明电极用于光入射。通常采用透明导电氧化物。一般地，所述透明导电氧化物由玻璃基底和氧化物薄膜(简称TCO)导电层组成。常规使用的TCO有ITO、FTO、AZO，但本申请不限于此。导电玻璃在使用前需清洗，例如用清洗剂(例如包括但不限于表面活性剂)、乙醇、丙酮、异丙醇和去离子水等超声清洗。
第二电极用于收集载流子，选自金属或碳衍生物，制备方法为本领域已知的技术方法，如热蒸镀法，厚度为20～1000nm。在本申请的一个具体实施例中，金属银为第二电极，通过蒸镀方法制成，厚度为50～120nm。
空穴传输层
空穴传输层用于收集和提取来自钙钛矿层的空穴。可使用本领域中常规使用的任何空穴传输层材料，可选使用满足上述HOMO能级匹配关系的空穴传输层材料。
可选地，例如，空穴传输层的材料为以下材料及其衍生物中的至少一种：聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、2,2’,7,7’-四[N,N-二(4-甲氧基苯基)氨基]-9,9’-螺二芴(Spiro-OMeTAD)、聚3-已基噻吩(P3HT)、三蝶烯为核的三苯胺(H101)、3,4-乙烯二氧噻吩-甲氧基三苯胺(EDOT-OMeTPA)、N-(4-苯胺)咔唑-螺双芴(CzPAF-SBF)、聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸)(PEDOT:PSS)、 聚噻吩、氧化镍(NiOx)、氧化钼(MoO 3)、碘化亚铜(CuI)、氧化亚铜(Cu 2O)等。
空穴传输层厚度范围可为5-300nm、可选为100-200nm。
电子传输层
电子传输层用于收集和提取来自钙钛矿层的电子。电子传输层材料可使用本领域中使用的任何电子传输层材料，可选使用满足上述HOMO能级匹配关系的电子传输层材料。
可选地，例如，电子传输层的材料为以下材料及其衍生物中的至少一种：[6,6]-苯基-C 61-丁酸甲酯(PC 61BM)、[6,6]-苯基-C 71-丁酸甲酯(PC 71BM)、富勒烯C60(C60)、富勒烯C70(C70)、二氧化锡(SnO 2)、氧化锌(ZnO)、二氧化钛(TiO 2)等
电子传输层厚度范围可为5-200nm、可选为20-100nm。
空穴传输层和电子传输层均可使用本领域中常用的方法制备。实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
I.钙钛矿太阳能电池的制备
实施I-1
【透明电极】
将规格为2.0cm×2.0cm的FTO导电玻璃表面依次用丙酮和异丙醇清洗2次，浸入去离子水中超声处理10min，再在鼓风干燥箱中干燥后，放置在手套箱中(N 2氛围)待用，此为透明电极。
【电子传输层】
使用匀胶机(LEBO EZ6-S，下同)在透明电极的FTO薄膜层上旋涂3重量％的SnO 2纳米胶体水溶液，旋涂时间为30秒。之后在恒 温热台上以150℃的温度加热15min，得到厚度为30nm的电子传输层。
【钙钛矿层】
钙钛矿层的制备过程如下：
步骤1：制备一维钙钛矿底层(第一覆盖层)
将上述已经形成有透明电极、电子传输层的样品放入真空镀膜机，在5×10 -4Pa的真空条件下，在电子传输层表面共蒸镀摩尔比为1：1.1的炔丙基铵碘盐和PbI 2，使这两种物质发生化合反应形成钙钛矿结构并沉积在样品表面，两种物质的蒸镀速率比为1:1(蒸镀速率为0.1埃/s)，得到一维钙钛矿底层，厚度为3nm；
步骤2：制备主体钙钛矿层
接着更换蒸发源为FAPbI 3单晶，在步骤1中得到的所述一维钙钛矿底层表面蒸镀FAPbI 3主体钙钛矿层，厚度为500nm；
步骤3：制备一维钙钛矿表层(第二覆盖层)
接着，使用匀胶机以5000rpm的速度在FAPbI 3主体钙钛矿层表面旋涂浓度为5mg/mL的炔丙基铵碘盐的异丙醇溶液，旋涂30s，之后在恒温热台上以100℃的温度加热10min，得到厚度为5nm的一维钙钛矿表层；
由此得到上下表面包覆的一维-三维-一维钙钛矿包覆层。
【空穴传输层】
使用匀胶机以5000rpm的速度在所得到的钙钛矿层上旋涂浓度为73mg/mL的Spiro-OMeTAD的氯苯溶液，旋涂时间为20秒，得到空穴传输层，厚度为150nm。
【第二电极】
将已经形成有透明电极、电子传输层、钙钛矿层和空穴传输层的样品放入真空镀膜机，在5×10 -4Pa的真空条件下，在所得到的空穴传输层表面蒸镀Ag，得到厚度为80nm的Ag电极，其为第二电极。
由此得到实施例I-1的钙钛矿太阳能电池。
实施例I-2至I-5
实施I-2至I-5的钙钛矿太阳能电池的制备以类似于实施例I-1操作，不同之处在于钙钛矿层的制备，具体参见表1。
实施例I-6
实施I-6的钙钛矿太阳能电池的制备与实施例I-1同样操作，不同之处在于钙钛矿层的制备，在步骤3之后进行如下操作：
步骤4：加保护层
接着，使用匀胶机以5000rpm的速度在步骤3中制备的一维钙钛矿表层表面旋涂浓度为5mg/mL的吡啶-2-羧酸铅的三氟乙醇溶液，使之完全覆盖表层表面，之后在恒温热台上以100℃的温度加热10min，得到保护层。
步骤5：加四周覆盖层(第三覆盖层)
接着，使用电动磨机(博世GSR120)对步骤4中得到的样品的保护层和钙钛矿层四周进行打磨清边，四边去除的保护层/钙钛矿层的宽度为1mm；然后，使用匀胶机以5000rpm的速度在所得样品的保护层表面旋涂浓度为5mg/mL的炔丙基铵碘盐的异丙醇溶液，使之能够流动到被打磨过的四周并完全覆盖四周，之后将该样品在恒温热台上以100℃加热10min，得到厚度约为5nm的一维钙钛矿四周覆盖层；
接着，滴加100μL的过量的三氟乙醇溶液，使之溶解保护层，然后使用匀胶机以6000rpm的速度旋转，将保护层和保护层上面的物质甩去，然后在恒温热台上以100℃加热5min；
最终得到由一维钙钛矿全覆盖的钙钛矿层。
实施例I-7和I-12
实施I-7至I-12的钙钛矿太阳能电池的制备与实施例I-6同样操作，不同之处在于参见表1。
实施例I-13至I-14
实施I-13至I-14的钙钛矿太阳能电池的制备与实施例I-1操作相同，不同之处仅在于一维钙钛矿包覆层表层和底层的厚度，参见下表。
对比例1
实施例I-15的钙钛矿太阳能电池的制备与实施例I-1操作相同，不同之处在于钙钛矿层的制备，如下：
将已经形成有透明电极、电子传输层的样品放入真空镀膜机，在5×10 -4Pa的真空条件下，在电子传输层表面蒸镀FAPbI 3底层，厚度为500nm，蒸发源为FAPbI 3单晶，得到钙钛矿层。
II.第二覆盖层能级匹配考察
实施例II-1至II-11
实施例II-1至II-11与实施例I-1类似，不同之处在于钙钛矿层的制备，具体参见表2。
III.第一覆盖层能级匹配考察
实施例III-1至III-9
实施例III-1至III-9与实施例I-1类似，不同之处在于钙钛矿层的制备，具体参见表3。
IV.电池性能测试
对各个实施例和比较例中的钙钛矿太阳能电池进行性能测试。
1.能量转换效率测试
对各实施例和比较例的钙钛矿太阳能电池测定能量转换效率。大气环境下，太阳光模拟光源使用AM1.5G标准光源，使用四通道数字源表(Keithley 2440)测量光源照射下电池的伏安特性曲线，得到电池的开路电压Voc、短路电流密度Jsc、填充因子FF(Fill Factor)，由此计算电池的能量转换效率Eff(Efficiency)。
能量转换效率如下计算：Eff＝Pout/Popt
＝Voc×Jsc×(Vmpp×Jmpp)/(Voc×Jsc)
＝Voc×Jsc×FF
其中Pout、Popt、Vmpp、Jmpp分别为电池工作输出功率、入射光功率、电池最大功率点电压及最大功率点电流。
在此测试中，开路电压Voc即为表2-3中的电池开压。
2.电池稳定性测试
对各实施例和比较例中的钙钛矿太阳能电池测试稳定性能。将电池放置在相对湿度RH为75～80％、环境温度为25～30℃的空气条件下，不避光放置至少800小时，根据上述测试方法测定其在放置前后的能量转换效率，计算放置800小时后的电池效率与初始效率的比值，作为电池稳定性能参数。
3.能级测试
在常温、常压下，使用型号为Escalab 250Xi(来自Thermo Scientific)的X射线-紫外光电子能谱仪(XPS-UPS)测试得到的各覆盖层的能带分布。
4.各覆盖层厚度测试
在常温、真空条件下，使用聚焦离子束(FIB)与高分辨扫描电子显微镜(SEM)耦合双束系统(FIB-SEM)对样品进行固定减薄、截面制样，进行厚度测试。
测试结果参见表1～3。
Figure PCTCN2022092191-appb-000001
Figure PCTCN2022092191-appb-000002
Figure PCTCN2022092191-appb-000003
一维钙钛矿包覆层的底层(第一覆盖层)的LUMO能级与其材料相关，第一覆盖层材料与碘化铅摩尔比越小，LUMO能级越小；
当一维钙钛矿底层的厚度为1～20nm且底层材料与碘化铅摩尔比为1:1.0～1:1.2时，能够实现更好的能量转换效率和电池开压；
一维钙钛矿包覆层的底层(第一覆盖层)的LUMO能级大于或小于、可选地小于主体钙钛矿层的LUMO能级且两者之差的绝对值在0～0.3eV范围内、可选在0.05～0.25eV范围内时，实现了更好的能量转换效率和电池开压；
电子传输层的LUMO能级小于或等于一维钙钛矿包覆层的底层(第一覆盖层)的LUMO能级且两者之差的绝对值在0～0.6eV范围内、可选在0.3～0.5eV范围内时，实现了更好的能量转换效率和电池开压。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (20)

  1. 一种钙钛矿太阳能电池，其在结构上依次包括透明电极、电子传输层、钙钛矿层、空穴传输层和第二电极，
    其中所述钙钛矿层包括主体钙钛矿层及覆盖在其表面和四周的一维钙钛矿包覆层，所述一维钙钛矿包覆层包括：
    位于主体钙钛矿层和电子传输层之间的第一覆盖层；
    位于主体钙钛矿层和空穴传输层之间的第二覆盖层。
  2. 根据权利要求1所述的钙钛矿太阳能电池，其中，所述一维钙钛矿包覆层还包括覆盖主体钙钛矿层四周的第三覆盖层。
  3. 根据权利要求2所述的钙钛矿太阳能电池，其中所述第一覆盖层、所述第二覆盖层、所述第三覆盖层的厚度各自独立地为1～20nm，可选2～5nm。
  4. 根据权利要求1～3中任一项所述的钙钛矿太阳能电池，其中，
    所述第一覆盖层的LUMO能级与所述主体钙钛矿层的LUMO能级之差的绝对值在0～0.3eV范围内，可选在0.05～0.25eV范围内。
  5. 根据权利要求1～4中任一项所述的钙钛矿太阳能电池，其中，
    所述第一覆盖层的LUMO能级大于或等于所述电子传输层的LUMO能级，且
    所述第一覆盖层的LUMO能级与所述电子传输层的LUMO能级之差的绝对值在0～0.6eV范围内，可选在0.3～0.5eV范围内。
  6. 根据权利要求1～5中任一项所述的钙钛矿太阳能电池，其中，
    所述第二覆盖层的HOMO能级大于或等于所述主体钙钛矿层的HOMO能级，且
    所述第二覆盖层的HOMO能级与所述主体钙钛矿层的HOMO能级之差的绝对值在0～0.3eV范围内，可选在0.05～0.1eV范围内。
  7. 根据权利要求1～6中任一项所述的钙钛矿太阳能电池，其中，
    所述第二覆盖层的HOMO能级小于或等于所述空穴传输层的HOMO能级，且
    所述第二覆盖层的HOMO能级与所述空穴传输层的HOMO能级之差的绝对值在0～0.3eV范围内，可选在0～0.15eV范围内。
  8. 根据权利要求1～7中任一项所述的钙钛矿太阳能电池，其中，所述第一覆盖层、所述第二覆盖层和所述第三覆盖层的覆盖材料各自独立地为选自以下物质或其衍生物中的至少一种的卤素盐：
    1-(2-吡啶基)-1H-吡唑、碘化吡咯烷、炔丙基铵阳离子、四丁基铵阳离子、2-氯代三乙铵阳离子。
  9. 根据权利要求1～8中任一项所述的钙钛矿太阳能电池，其中所述第一覆盖层和所述第二覆盖层之一由所述覆盖材料和卤化金属盐形成，可选地，所述覆盖材料和卤化金属盐的摩尔比在1:0.9～1:1.3范围内，可选在1:1.05～1:1.2范围内。
  10. 根据权利要求9所述的钙钛矿太阳能电池，其中所述卤化金属盐选自碘化铅、溴化铅或氯化铅中的至少一种，可选为碘化铅。
  11. 一种制备钙钛矿太阳能电池的方法，包括制备或准备透明电极的步骤、制备电子传输层的步骤、制备钙钛矿层的步骤、制备空穴传输层的步骤、制备第二电极的步骤，其中，
    所述钙钛矿层包括主体钙钛矿层及覆盖在其表面和四周的一维钙钛矿包覆层，所述一维钙钛矿包覆层包括：
    位于主体钙钛矿层和电子传输层之间的第一覆盖层；
    位于主体钙钛矿层和空穴传输层之间的第二覆盖层。
  12. 根据权利要求11所述的制备钙钛矿太阳能电池的方法，其中，制备钙钛矿层的步骤包括以下操作：
    (1)在电子传输层或空穴传输层上涂覆覆盖层材料以及卤化金属盐，得到底层覆盖层，
    (2)在底层覆盖层上涂覆用于制备主体钙钛矿的材料，得到主体钙钛矿层，
    (3)在主体钙钛矿层上涂覆覆盖层材料，得到表层覆盖层，
    其中所述底层覆盖层和所述表层覆盖层中任意一个为第一覆盖层，另一个为第二覆盖层。
  13. 根据权利要求11或12所述的制备钙钛矿太阳能电池的方法，其中，还包括制备覆盖主体钙钛矿层四周的第三覆盖层的步骤，该步骤具体包括以下操作：
    (4)在表层覆盖层上涂覆保护层材料，得到保护层，
    (5)在保护层上添加覆盖层材料的溶液，使之流动到主体钙钛矿层和保护层的四周以完全覆盖所述四周，加热，得到四周覆盖层，此即为第三覆盖层，
    (6)除去保护层。
  14. 根据权利要求13所述的制备钙钛矿太阳能电池的方法，其中，(1)、(3)、(5)中的覆盖层材料各自独立地为选自以下物质或其衍生物中的至少一种的卤素盐：
    1-(2-吡啶基)-1H-吡唑、碘化吡咯烷、炔丙基铵阳离子、四丁基铵阳离子、2-氯代三乙铵阳离子。
  15. 根据权利要求11～14中任一项所述的制备钙钛矿太阳能电池的方法，其中，在(1)中，所述覆盖材料和所述卤化金属盐的摩尔比在1:0.9～1:1.3范围内，可选在1:1.05～1:1.2范围内。
  16. 根据权利要求11～15中任一项所述的制备钙钛矿太阳能电池的方法，其中，所述卤化金属盐选自碘化铅、溴化铅或氯化铅中的至少一种，可选为碘化铅。
  17. 根据权利要求13～16中任一项所述的制备钙钛矿太阳能电池的方法，其中，所述涂覆以旋涂、共蒸镀或蒸镀的方式进行，可选地，在(4)中，所述涂覆以旋涂的方式进行，旋涂完毕后进行加热，得到保护层。
  18. 根据权利要求13～17中任一项所述的制备钙钛矿太阳能电池的方法，其中，(6)中，使用溶剂溶解保护层，可选地，溶解保护层的溶剂为三氟乙醇；然后将保护层及保护层上面的物质通过旋转的方式甩去。
  19. 根据权利要求13～18中任一项所述的制备钙钛矿太阳能电池的方法，其中，所述保护层材料为吡啶-2-羧酸铅。
  20. 一种用电装置，其包括权利要求1-10中任一项所述的钙钛矿太阳能电池或根据权利要求11-19中任一项所述的制备钙钛矿太阳能电池的方法制备的钙钛矿太阳能电池。
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